Flavor-stable rearranged fats from domestic oils



2,859,120 Patented Nov. 4, 1958 United States Patent OfiiceFLAVOR-STABLE REARRANGED FATS FROM DOMESTIC OILS Walter M. Cochran,Highland Park, Claude W. Lantz,

La Grange, and Melvin L.'0tt, Park Ridge, 111., assignors to The GliddenCompany, Cleveland, Ohio, a corporation of Ohio No Drawing. ApplicationJuly 12, 1954 Serial No. 442,882

3 Claims; (199-118 This invention relates to novel fats. prepared frommixtures of domestic oils by hydrog'enating such oils of the mixture astend to revert, thereby to overcome flavorreversion tendencies, and thenrearranging the mixture. The use of this combination of treatmentspermits extensive expansion of the usage in commerce of various domesticoils and fats which heretofore have enjoyed limited usage in edibleproducts and/ or have been considered inappropriate for web edibleproducts. Accordingly, the combination of treatments imparts increasedflexibility and latitude in selecting available domestic oils and fatsfor conversion into high grade edible products.

Accordingly, it is an object of this invention to provide novelflavor-stable rearranged fats derived from mixtures of availabledomestic triglyceride'raw materials.

It is another object to provide a novel process for preparing the fatsdescribed in the preceding object.

These and other objects will be apparent from the following descriptionof the invention.

Various edible grade beef fats such as oleo stearine, tallow, oleo'oil,various fish oils, various vegetable oils such as soybean oil, corn oil,and other oils available in the continental United States andneighboring countries of North America have long been known to be of thereverting type; that is, by their nature they tend to turn rancid andhence to revert to their original crude or natural flavor. Otherdomestic oils such as cottonseed oil, peanut oil, lard, sesame oil andothers are fairly stable in flavor and do not revert easily to theircrude or natural flavor. The latter oils have been used widely in edibleproducts for this reason, but the demand for them and the resultingprice level induces the use of other domestic triglycerides which can,by appropriate processing, be used in their place. The reverting oilsmentioned above have not been used as widely in edible products as theirchemical nature should permit, largely because of their flavor-reversiontendencies. It has long been known that the reversion tendencies areconnected in some manner with unsaturation in the 6-24 carbon fatty acidradicals of at least some of the triglycerides which constitute theoils, and it has long been known that moderate to extensivehydrogenation of the oils reduces the unsaturation and overcomes thereversion tendencies. Appropriate hydrogenation (suflicient to impartflavor-stability equal to 94 hydrogenated cottonseed oil) has therebymade it possible to use many of the oils in edible products.Nevertheless, hydrogenation has the efiect of hardening the oils, and innumerous'instances the amount of hydrogenation necessary to overcomeflavor reversion has so hardened the oils as to make them of limitedusefulness in edible products-such as shortenings, hard butters, cookingoils, etc. We have now discovered that such hardening can be overcome byrearranging each of the hydrogenated oils or mixtures thereof inadmixture with other domestic nonreverting oils. The latter can benaturaLnon-revert- 'ing oils of the kinds mentioned hereinabove, and/orcan be normally-reverting oils which have been hydrogenatedsuflicien'tlytobeflavor stable,'i. e., until'they possess a outhydrogenating any stability against reversion equal .to 94 hydrogenatedcottonseed oil. The mixtures can be selected as to kinds and proportionsof oils present, and as toamount of residual unsaturation, so that afterrearrangement they will yield a wide range of physical properties in thetreated mass of fat. 7 Thus the starting mixture canbe selected on thebasis of principles and characteristics :available to those skilled inthe art sothat on rearrangement the mixture will'give fats useful as orin shortenin'gs, hard butters, cooking oils, specialty fat products forthe :food industry, etc. Accordingly,' the present processatfordswidened latitude in the choice of the raw or starting materials whichcan be used to prepare almost any of the more common edible fatproducts, and hence imparts flexibility in their manufacture and lessdependence on fluctua tions in supplyand price of the oils commonlydemanded in the past. I

' The benefits of the invention in', the shortening field areillustrated :by the following considerations. 7

Most all shortenings are prepared by adding various amounts of stearineto a soft uuhydrogenated or partially hydrogenated 'base oil'. The baseoil is stable against oxidation or reversion only to the extent to whichthe poorest'oil used' therein tends to be stabilized by the amount ofhydrogenation permissible. If, for instance, the base oil were to be ablend of soybean and cottonseed oil and a final congeal point of 25 wasrequired, the base oil under'normal'hydrogenation would only be asstable as 25 soybean oil. With our invention, when a blend of two oilsisto be used to make the base stock, we hydrogenate'the reverting typeto apoint where (a) the stability against reversion is at least equal to 94hydrogenated cottonseed oil, and .(b) the hardness is appropriate forthe next step. We then rearrangethis material in admixture with theselected non-reverting component, it being understood that the latteralready ness which is known by experience to give the rearranged blendthe desired congeal point; In many instances this congeal point can bereached on rearrangement .withof the oil(s) except thenormallyrreverting oil. 4 p a '1 11 Following area few examples of shorteningbase, oils which can be prepared in this manner The intent and result ineach case is to stabilize the final rearrangedjproductagainst reversionby highly hydrogenating the unstable component prior to rearrangemenLIRearrangement of the blends in each case is necessary and/ordesirablebecause without rearrangement the mixtures. would'be toohard'to useas shortening base oils. I

(1) 50%cottonseed oil hardened to2-0- congeal 50% soybean oil hardenedto 35 congeal (2) 20 congeal cottonseed oil 25% tallow stearine (3) 75liquid peanut oil 25% tallow stearine 40% liquid peanut oil 60% 40congeal soybean oil liquid lard- 20% fish oil stearine 60% liquid lard40% 10 1.1 V. drop'hydro tallow The rearrangement treatment (also knownas interesterification) which we contemplate is that which is commonlyreferred to as low-temperature rearrangement, using such catalystsas areknown to be'etfective at temperatures below about 250 F., usingtemperatures;

which continuously maintain the massof fat in a liquid or single-phasecondition, and using other operating conditions favorable to theselected catalyst. Such rear rangement treatment is one of shortduration, but one 3 I which gives fully rearranged material at a lowoverall processing cost.

As indicated above the catalyst is a low temperature rearrangementcatalyst such as the alkali metal alkoxides 'having'up to4'carbon'atoms, alkali metal hydrides such as'sodium' hydride, andnumerous others such'as are de-. scribed -in the Eckey U. S.- Patent No.2,442,536. Other alkaline compounds such as lithium aluminum hydrideand-calcium hydride have been found by us to be inefiective, as havesuch catalysts as aluminum isopropylate. v ve'aredaware ofthe Gooding U.SJPatent 2,309,949 in which a variety'ofalkaline-reacting compounds areemployed in combination with hydroxyl-carrying materials, lbufi suchcatalysts and/or the high reactiontemperatures involved inrtheir uselead toless desirable results than wezobtainw i. e

1 Small amounts of the low' temperature'rearrangement catalysts'areemployed in the treatment, as little as .02% of sodium methoxidebyaweight onthe mixture of glycerides-being effective when conditions aresuch that it is in an active condition. 'Most of the catalysts induce anexothermic-reaction and :such exothermicity becomes increasinglydiflicult towork with as the. amount of catalyst is increased. Moreover,lossesof glycerides then tend to be increased and moresaponificationtends to occur For these 'reasons we""avoid the use of more'than about1% of catalyst. We prefer to use. between about 0.1% and 0.5% of suchactive catalysts'as sodium methoxidasodium ethoxide or sodium'rhydride,and prefer a chemically equivalent percentage of other active lowmps c tr c lysts The catalyst iseasily destroyed or inactivated by water,moisture, carbon dioxide andair; Accordingly, in order to providetreating conditions whichjare favorable to activity onthe part of thecatalyst, the mixture of triglycerides should be thoroughly dry, andcontact with the moistureand carbon .dioxidepf the air must beprevented, We .havefound that aninert atmosphere such QSQP. i ro n r vauum s very effective W an inert gaseous atmosphere of hydrogen ornitrogen is maintained over the mixture of glycerides, the treatment canbe effectively carried out in-a loosely-covered containerl Preferably,however, the treatment is conducted in a vacuum chamber since by heatingthe mass to expeditious reaction temperatures in a vacuum of around 0.1to 0.2 inch of mercury or lower, the glycerides can be driedeffectively. Nitrogencan then be introduced for agitation andblanket'ing pu'rposesto reduce the vacuum to"about'..1.5'inches gauge;pressure. Mechanical agitation can also. be used. The container may beof iron, stainless 'steeLfYglass for aluminum. However, when aluminum isused, the amount of catalyst must generally b' f r s'ed- I a 'A t Thecatalyst is also destroyed by free acids and by peroxides. Accordingly,the glycerides which are to be treatedshould have been refined inadvance with alkalis or otherwise'to reduce the free fatty acid contentto about .05 or lower, and to eliminate peroxides as far as possible. Itshould be understood that the provision of refined triglycerides and ofother conditions favorable to the catalyst is done mainly in theinterest of economizmg the catalyst. The consequence of not making suchprovisions is simply thatv'the' quantityof catalyst which must beintroduced to overcome all such unfavorable factors is wasted.

As indicated above, the temperature of the catalytic treatment can bevaried over an appreciable range. When solvents are employed,temperatures-as low as room temperature have been employed successfully.Whenthe treatment is conducted in the absence of solvents, thetemperature should at least be high 'en'ough. to maintain.

the mass in the liquidipha'se throughout the' catalytic .treatmenu, Theminimum temperature will, of course, then depend on the particularmixture of triglycerides which is being treated. Temperatures as high as250 have been used successfully in vacuum equipment in the ab- 4; i; fsence of solvents, but we prefer to use temperatures around 200240 F. insuch vacuum equipment as they lead to low. losses of material and to theformation of but little soap. Temperatures above about 250 F. areavoided because of catalyst decomposition and because of i theexothermicity of theireaction and the disadvantageous results attendantthereon, as mentioned above.

The eifectiveness of the catalyst and of the treatment can bedetermined'by'the changed physical properties of the mass, but we havealso found that it is easily determined by the color. of the mass ofglycerides. The color of the mass changes from its original color to areddish-brown color when the rearrangement reactions have beencompleted. If no such color change is observed within a few minutesafter the catalyst has been added, it signifies that something hasdeactivated the catalyst. Frequently theinitialaddition of the catalystalmost cures the difiiculty, and the rearrangement will be found tooccur on the further addition of a small quantity of catalyst. Likewise,when only a .slight color change is observed, it may signify that the.catalyst'wasmitially active but was soon inactivated. A furtheraddition-of .catalyst will then cause th reaction to go to completion.

We have observed that the rearrangement reaction goes to'completion inthe space; of a few minutes if sutficient active catalyst is present.The addition of'more catalyst under such conditions produces no furtherchange, not q o n he mass fqr a p o nged cause any material change,

After the catalytically-induced rearrangement reaction has been gom lemas cancoo ed suific enfly to permit it to be washed with water ordilute acidsl so as to fi m s th a a t, Su r a hiu s p f rably done attemperatures around 170-180 F. since there is limet nd nq t su hxt m raurss f qr an e ulsio t be formedh W hed m rial a thsn'bez St ti and thewater separatedfr om the massoftreat oi l; The oil can then be dried byapplyingva uurn w th or without further heating." The drying operationcan,:'o

course, be done in any of the other wayjs well known to those skilled inthe art.

invention: V

' EXAMPLE. ,1

A blend of liquid lard and l0-%lta llow stearine was rearranged withsodium methoxide 'at 220 Rand deodorized.

The deodorizedrearranged fat mixture had ,a good bland flavor and aSchall test of 6'days. be detected while running this test.

EXAMPLE 2 1 b e ta low having h Properties lis e b ow w refined andbleached and then @waspartially hardened No animal odor could asR-io'sY1.35-

Free Fatty Acids (Oleie), percent Refractive Index at48" 0.- CongealPoint, C Wiley Melting Point, Iodine Value.-

Therefined, bleached, edible tallow used in the h idein ing was 0.2R.-2Y.0.02f6% free fatty acids. Using the resui ing pa tially hardened.tallow, 10 p r s t rcflane Pfiriod of time The followlng examplesillustrate the principles of our Properties of Blend Before Re- AfterReearrangement ment Refractive Index at 43 (3---. 46.0 45. 6 CongealPoint, C 28.3 27. 7 Wiley Melting Point, F 99.0 98.0 Capillary MeltingPoint, F 106. 7 102. 2

It will be observed that the low-temperature rearrangement significantlylowered the congeal point and melting points EXAMPLE 3 A blend of liquidlard plus hydrogenated tallow duplicating the properties of the 90l0mixture of Example 1 was sought. A mixture of 60% liquid lard with 40%of the partially-hardened tallow of Example 2 was found to accomplishthis result. This mixture was rearranged at 220 F. with 0.2% sodiummethoxide to give the following properties:

Both fat products (before and after rearrangement) were In:baking testson a pound cake formula g'ivenxbeldw' the following results were securedwhen the shortening was the rearranged product of Example 1 plasticizedwith 10% of tallow stearine:

Sp. Gr. Temp., Batter Volumn, Texture degrees cc.

.768 74 Smooth 1, 130 Fine and even; Very nice texture and top. .777 77Smooth 1, 155 Fine and even, Exceptlonally nice; Very smooth top.

Durkee standard pound cake recipe Lbs. Ozs

Gran. Sugar 1 Shortening 8 Whole Eggs 8 Salt V Cream for 20 minutes onsecond speed, scrape bowl.

Liquid M 9 Gran. Suear 1 Add to above: Mix 10 rev. on first speed,scrape bowl.

Cake Flour 1 Add to above: Mix one minute on first speed, scrape bowland mix Plastic Fat Plus Sp. Gr. Temp., Batter Volume, Displace- TextureF. cc. ment 8% SGF 853 72 Smoothl, 410 1, 135 Fitnemicepeaked op. Y 2 4%DPI 18-40 961 72 Smooth- 1, 455 l, 165 Slightly coarse, 1slightly pitteds A commercial mono-diglyceride product of the Durkee Division of TheGlidden Company, approximately 40% mouoglycerides-MZ, diglycerid b Acommercial mono-diglyceride product of Distillation Products Company,Inc, approximately 18% monoglycerides40% diglycerides. deodorized andSchall tests were determined: Standard Durkee white cake formula Before-Cake flour ounces 12 /2 Emulsified Shortenin rln 10 Schall Test at F 117 days- Cream for 2 minutes on low speed, scrape bowl. Neither fatproduct had lardy or tallowy flavors and no flsugar a 28 tallowy odorsdeveloped during the Schall test. e 0 71,2

Skim milk powder do.. 2% EXAMPLE 4 S all t in In a standard wet creamingtest for non-emulsified Baking Powder grams 35 5 shortenings thefollowing materials are mixed together Water and tested as stated: Creamfor 2 minutes on low speed, scrape bowl.

530 grams 6/X sugar Egg white mmce-sn 16 g i if gi Cream for 2 minutesonlow speed, scrape bowl. o Water unces 7 b All ingredients at 75 F.Vanilla an 14 Place these ingredients in 3-quart Hobart bowl, mix /fiminute at first speed, scrape down bowl and beater. Mix at second speedfor 25 additional minutes, getting Specific Gravity and Temperature andscraping down well at 5, 15 and 25 minutes.

In such creaming test of the rearranged fat prepared in Example 1, thefollowing data was secured:

5 Min. 15 Min. 25 Min.

Sp. Gr. Temp, F. Sp. Gr. Tgrilp, Sp. Gr. Temp, F.

All ingredients75 F.

Cream for 4 minutes on low speed. Record specific gravity andtemperature. Scale 14 ounces per 8-inch layer pans. Bake 21 minutes at360 oven.

EXAMPLE 5 Sixty parts of 20 congeal hydrogenated cottonseed oil and 40parts of 35 congeal hydrogenated soybean oil (I. V. about 65) were mixedtogether and then were rearranged by treatment with 0.2% sodiummethoxide at 220 F. A comparison of the properties of the blend beforeand a fter rearrangement. is given 'in the following Before-Re A'fterRe- Property arrangearrangen'ient ment Refractive Index at 48 C 48. 0048. 00 Cougeal"Point; G: 28;2' 2b". 0" Wiley Melting Point, F 98.0 91.5

Examples 5 and 6' illustrate the merits in rearranging blends of oilscontaining one revertible-type oil which has been hydrogenated toimprove its stability. It will be noted that the rearranged blends havea Wiley melting point around 92 R, which is a common Wiley forallpurpose shortening oil. It will be noted, however, that withoutrearrangement neither blendwould have met this requirement. rah-aveproduced the same Wiley from refined, non-rearranged soybean oil,acongeal point of 26 and an iodine value of 76 would be needed. Thus itwill be'apparent that the rearrangement has permitted the use ofsoybeanoil having a congeal point 9 higher and an iodine value 11 points lower.Soybean oil of these properties is known to be practicallynon-reverting; Consequently, rearrangement of the blends has permittedthe use of stabilized soybean oil and the preparation of flavorstableall purpose oils where without rearrangement the blends wouldnecessarily have had to contain soybean oil of undesirable revertingtendencies.

Examples 1-3 illustrate similar benefits as the result of rearrangingthe blends: The products of those examples are equal in flavor stabilityto straight unhydrogenated lard.- In other words, the introduction oftallow has not decreased the stabilitycharacteristics of the base oil,and rearrangement of the blends has permitted its use without producinga product much harder than natural lafd. For p urpose s of comparison,the following properafigenaar are given:

ties of lar'dibefdf a'ri'cl after rearr Before Re- After Re- Propertyarrange arrange ment ment Congeal Point, 1Q 26. 5 24, 5 Wiley MeltingPoint, 'F I03. 0 96; 0 Capillary Melting Point, F 107.0 105.0

Y subsequently destroying said catalyst; and converting the i 8 It willbe apparentriers we: foregbing eitam'p es descriptionof ourinvenrionthatthe present inven pro? vides the shortening maauracttirerelsewhere-working in" the triglyceride oil' industry with significantlymore fl exi bility" in the choice of his raw materials and in the. prseniens'therbf which he can use to prepare productsoffprhdeteriiiinetl'pliysical properties and keeping qualities. t

This application is a 'continuation=in=partof' our pending applicationSerial No. 356,962, -filed- May 25; 193andi entitled Rear'rangedFatProductsandl rocessl That apr plication describes and claimsapr'oc'es's aiialogoiis t th? present oneinwhich atleast oneflayonstabilized par tially liyc'frogenatedg; norrfia'llfireve'rting oil isrearranged ing-type product suitable for frozen desserts anddtlie'r'specialty products.

Having described-dun invention";- what clairntis'a 1. The process ofpreparing" novel flfat pioducts Emir reverting andnen revertifigtriglyceridefats, said proc'e'ss comprising the steps of: providing afirst component -com-* prisiiig'u'nsaturated triglyceride fatwhichnorm'allyiturrisf rancid and" develops'unpleasan't fla'vorbyr'eason th'fereofi: partially hydrogenating said first componentsufi'icien'tlyf to impart thereto a stability against reversion at leastequal to 94 hydrogenated cottonseed oil; blending said hydrogenatedfirst triglyceride component with a second and different fat componentcomposed essentiallyof'ti'i j glycerides of the normally non-reverting,non-rancidify=z. ing type; and'catalytically rearranging-said blended'com ponents at temperaturesbelow about250 F. whilecon tinuouslymaintaining them in single-phase condition n1 contact with alow-temperature rearrangement catalyst under conditions favorable tocomplete rearrangement and to rearrangement activity on the part of saidcatalyst;

so-treated mass of completely rearranged triglycerides to a single fatproduct in an edible state.

2. The process as claimed in claim 1 wherein said normally non-revertingtriglyceride component is composed of domestic triglycerides of naturalorigin 3. As anovel composition of matter a rearranged, flavorstabletriglyceride product prepared by the process of claim 2.

References Cited in the file of this patent I UNITED STATES PATENTS

1. THE PROCESS OF PREPARING NOVEL FAT PRODUCTS FROM REVERTING ANDNON-REVERTING TRIGLYCERIDE FATS, SAID PROCESS COMPRISING THE STEPS OF:PROVIDING A FIRST COMPONENT COMPRISING UNSATURATED TRIGLYCERIDE FATWHICH NORMALLY TURNS RANCID AND DEVELOPS UNPLEASANT FLAVOR BY REASONTHEREOF, PARTIALLY HYDROGENATING SAID FIRST COMPONENT SUFFICIENTLY TOIMPART THERETO A STABILITY AGAINST REVERSION AT LEAST EQUAL TO 94*HYDROGENATED COTTONSEED OIL, BLENDING SAID HYDROGENATED FIRSTTRIGLYCERIDE COMPONENT WITH A SECOND AND DIFFERENT FAT COMPONENTCOMPOSED ESSENTIALLY OF TRIGLYCERIDES OF THE NORMALLY NON-REVERTING,NON-RANCIDIFYING TYPE, AND CATALYTICALLY REARRANGING SAID BLENDEDCOMPONENTS AT TEMPERATURES BELOW ABOUT 250*F. WHILE CONTINUOUSLYMAINTAINING THEM IN SINGLE-PHASE CONDITION IN CONTACT WITH ALOW-TEMPERATURE REARRANGEMENT CATALYST UNDER CONDITIONS FAVORABLE TOCOMPLETE REARANGEMENT AND TO REARRANGEMENT ACTIVITY ON THE PART OF SAIDCATALYST, SUBSEQUENTLY DESTROYING SAID CATALYST, AND CONVERTING THESO-TREATED MASS OF COMPLETELY REARRANGED TRIGLYCERIDES TO A SINGLE FATPRODUCT IN AN EDIBLE STATE.